Poly[diaqua­bis[μ2-2,4-(dichloro­phenoxy)­acetato-κ2O:O′]iron(II)]

Pan, W.-B.; Xu, X.-H.; Huang, X.-H.; Zeng, R.-H.

doi:10.1107/S1600536808029279

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page m1287

doi:10.1107/S1600536808029279

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Poly[diaquabis[μ₂-2,4-(dichlorophenoxy)acetato-κ²O:O′]iron(II)]

Wei-Bo Pan,^a Xiao-Hong Xu,^a Xiao-Hui Huang ^a and Rong-Hua Zeng ^a,^b ^*

^aSchool of Chemistry and the Environment, South China Normal University, Guangzhou 510006, People's Republic of China, and ^bKey Laboratory of Electrochemical Technology, of Energy Storage and Power Generation in Guangdong Universities, Guangzhou 510631, People's Republic of China
^*Correspondence e-mail: zrh321@yahoo.com.cn

(Received 15 August 2008; accepted 12 September 2008; online 20 September 2008)

In the title compound, [Fe(C₈H₅Cl₂O₃)₂(H₂O)₂]_n, the Fe^II atom is located on an inversion center. It is coordinated by four O atoms from four 2,4-dichlorophenoxyacetate ligands and two water molecules, displaying a distorted octahedral geometry. The carboxylate groups of the 2,4-dichlorophenoxyacetate ligands link the Fe atoms, forming a polymeric layered network in the bc plane. Intralayer O—H⋯O hydrogen bonds enhance the stability of the two-dimensional network.

Related literature

For background on supramolecular networks, see: Eddaoudi et al. (2001 ); Rizk et al. (2005 ).

Experimental

Crystal data

[Fe(C₈H₅Cl₂O₃)₂(H₂O)₂]
M_r = 531.92
Monoclinic, P 2₁ /c
a = 17.604 (2) Å
b = 7.3122 (8) Å
c = 8.0312 (9) Å
β = 94.258 (2)°
V = 1031.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 296 (2) K
0.23 × 0.21 × 0.20 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.756, T_max = 0.782
5059 measured reflections
1849 independent reflections
1675 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.097
S = 1.05
1849 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Fe1—O3ⁱ	2.1654 (17)
Fe1—O2	2.1697 (16)
Fe1—O1W	2.2297 (18)

O3ⁱ—Fe1—O2	80.18 (6)
O3ⁱⁱ—Fe1—O2	99.82 (6)
O3ⁱ—Fe1—O1W	89.36 (7)
O3ⁱⁱ—Fe1—O1W	90.64 (7)
O2ⁱⁱⁱ—Fe1—O1W	91.25 (7)
O2—Fe1—O1W	88.75 (7)
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1W—H1W⋯O1^iv	0.82	2.41	3.051 (3)	135
O1W—H2W⋯O3ⁱⁱⁱ	0.82	2.08	2.797 (3)	145
Symmetry codes: (iii) -x, -y+1, -z+1; (iv) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: APEX2 (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablock global. DOI: 10.1107/S1600536808029279/hy2149sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808029279/hy2149Isup2.hkl

checkCIF report

Comment top

The design, synthesis, characterization and properties of supramolecular networks formed by using functionalized organic molecules as bridges between metal centers are of great interest (Eddaoudi et al., 2001; Rizk et al., 2005). As a building block, 2,4-dichlorophenoxyacetate is an excellent candidate for the construction of supramolecular complexes. Recently, we obtained the title compound, a new coordination polymer.

In the title compound, the Fe^II atom is located on an inversion center and coordinated by four O atoms from four 2,4-dichlorophenoxyacetate ligands and two water molecules in an octahedral geometry (Fig. 1; Table 1). The Fe^II atoms are linked by 2,4-dichlorophenoxyacetate ligands to form a polymeric layered network in the bc-plane (Fig. 2). The two-dimensional network is further stabilized by intralayer O—H···O hydrogen bonds involving the coordinated water molecules and the O atoms from the ligands (Table 2). The adjacent Fe···Fe separation is 5.431 (4) Å.

Related literature top

For background on supramolecular networks, see: Eddaoudi et al. (2001); Rizk et al. (2005).

Experimental top

A mixture of FeCl₂ (0.127 g, 1 mmol), 2,4-dichlorophenoxyacetic acid (0.221 g, 1 mmol), NaOH (0.04 g, 1 mmol) and water (10 ml) was stirred vigorously for 20 min, and then sealed in a 20 ml Teflon-lined stainless steel autoclave. The autoclave was heated to and maintained at 433 K for 2 d, and then cooled to room temperature at 5 K h^-1 to afford red block crystals.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound, together with symmetry-related atoms to complete the coordination units. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (i)-x, 1-y, 1-z; (ii) x, 1/2-y, 1/2+z; (iii) -x, 1/2+y, 1/2-z.]
	Fig. 2. View of the two-dimensional network in the title compound.

Poly[diaquabis[µ₂-(2,4-dichlorophenoxy)acetato-κ²O:O']iron(II)] top

Crystal data top

[Fe(C₈H₅Cl₂O₃)₂(H₂O)₂]	F(000) = 536
M_r = 531.92	D_x = 1.714 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6377 reflections
a = 17.604 (2) Å	θ = 1.7–28.0°
b = 7.3122 (8) Å	µ = 1.29 mm⁻¹
c = 8.0312 (9) Å	T = 296 K
β = 94.258 (2)°	Block, colourless
V = 1031.0 (2) Å³	0.23 × 0.21 × 0.20 mm
Z = 2

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1849 independent reflections
Radiation source: fine-focus sealed tube	1675 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scan	θ_max = 25.2°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −21→17
T_min = 0.756, T_max = 0.782	k = −8→8
5059 measured reflections	l = −9→9

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.0473P)² + 1.0193P] where P = (F_o² + 2F_c²)/3
1849 reflections	(Δ/σ)_max < 0.001
137 parameters	Δρ_max = 0.49 e Å⁻³
0 restraints	Δρ_min = −0.48 e Å⁻³

Crystal data top

[Fe(C₈H₅Cl₂O₃)₂(H₂O)₂]	V = 1031.0 (2) Å³
M_r = 531.92	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 17.604 (2) Å	µ = 1.29 mm⁻¹
b = 7.3122 (8) Å	T = 296 K
c = 8.0312 (9) Å	0.23 × 0.21 × 0.20 mm
β = 94.258 (2)°

Data collection top

Bruker SMART APEXII CCD area-detector diffractometer	1849 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1675 reflections with I > 2σ(I)
T_min = 0.756, T_max = 0.782	R_int = 0.021
5059 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.097	H-atom parameters constrained
S = 1.05	Δρ_max = 0.49 e Å⁻³
1849 reflections	Δρ_min = −0.48 e Å⁻³
137 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Fe1	0.0000	0.5000	0.5000	0.03073 (17)
Cl1	0.30460 (6)	0.78166 (12)	0.11801 (14)	0.0735 (3)
Cl2	0.46770 (6)	0.2467 (2)	0.43433 (14)	0.0928 (4)
C5	0.24797 (14)	0.4477 (4)	0.1746 (3)	0.0356 (6)
C4	0.31062 (16)	0.5621 (4)	0.1975 (4)	0.0431 (6)
C1	0.32151 (18)	0.2103 (5)	0.3170 (4)	0.0530 (8)
H1	0.3253	0.0913	0.3575	0.064*
C6	0.25386 (16)	0.2715 (4)	0.2358 (4)	0.0435 (6)
H6	0.2122	0.1932	0.2226	0.052*
C2	0.38251 (18)	0.3256 (5)	0.3371 (4)	0.0565 (8)
C3	0.37794 (18)	0.5028 (5)	0.2792 (4)	0.0553 (8)
H3	0.4195	0.5812	0.2948	0.066*
O1	0.18551 (10)	0.5189 (2)	0.0859 (2)	0.0385 (4)
O2	0.07809 (9)	0.4569 (2)	0.3070 (2)	0.0323 (4)
C7	0.07058 (13)	0.3655 (3)	0.1753 (3)	0.0277 (5)
C8	0.12459 (15)	0.3979 (4)	0.0403 (3)	0.0367 (6)
H8A	0.1456	0.2812	0.0092	0.044*
H8B	0.0958	0.4467	−0.0575	0.044*
O3	0.01927 (10)	0.2497 (2)	0.1419 (2)	0.0407 (4)
O1W	0.09385 (11)	0.6384 (3)	0.6535 (2)	0.0416 (4)
H1W	0.1227	0.6879	0.5917	0.062*
H2W	0.0708	0.7130	0.7070	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Fe1	0.0341 (3)	0.0280 (3)	0.0304 (3)	0.00233 (19)	0.0045 (2)	0.00195 (19)
Cl1	0.0771 (6)	0.0489 (5)	0.0935 (7)	−0.0269 (4)	−0.0007 (5)	0.0116 (4)
Cl2	0.0567 (6)	0.1397 (11)	0.0803 (7)	0.0293 (6)	−0.0068 (5)	0.0080 (7)
C5	0.0338 (13)	0.0400 (13)	0.0344 (13)	−0.0029 (11)	0.0113 (10)	−0.0048 (11)
C4	0.0430 (15)	0.0433 (15)	0.0439 (15)	−0.0095 (12)	0.0089 (12)	−0.0045 (12)
C1	0.0574 (19)	0.0538 (18)	0.0493 (17)	0.0108 (15)	0.0136 (14)	0.0055 (14)
C6	0.0434 (15)	0.0410 (15)	0.0474 (16)	−0.0046 (12)	0.0119 (12)	0.0001 (12)
C2	0.0435 (17)	0.081 (2)	0.0451 (17)	0.0115 (16)	0.0060 (13)	−0.0031 (16)
C3	0.0384 (16)	0.073 (2)	0.0546 (18)	−0.0126 (15)	0.0041 (13)	−0.0088 (16)
O1	0.0344 (10)	0.0370 (10)	0.0444 (10)	−0.0064 (7)	0.0052 (8)	0.0011 (8)
O2	0.0327 (9)	0.0342 (9)	0.0305 (9)	−0.0017 (7)	0.0056 (7)	−0.0074 (7)
C7	0.0291 (12)	0.0234 (11)	0.0305 (12)	0.0049 (9)	0.0025 (9)	0.0012 (9)
C8	0.0369 (13)	0.0429 (15)	0.0306 (12)	−0.0072 (11)	0.0052 (10)	−0.0047 (11)
O3	0.0423 (10)	0.0358 (10)	0.0456 (11)	−0.0128 (8)	0.0140 (8)	−0.0149 (8)
O1W	0.0415 (11)	0.0412 (10)	0.0419 (10)	−0.0042 (9)	0.0030 (8)	−0.0053 (9)

Geometric parameters (Å, º) top

Fe1—O3ⁱ	2.1654 (17)	C1—H1	0.9300
Fe1—O3ⁱⁱ	2.1654 (17)	C6—H6	0.9300
Fe1—O2ⁱⁱⁱ	2.1697 (16)	C2—C3	1.377 (5)
Fe1—O2	2.1697 (16)	C3—H3	0.9300
Fe1—O1W	2.2297 (18)	O1—C8	1.417 (3)
Fe1—O1Wⁱⁱⁱ	2.2297 (18)	O2—C7	1.250 (3)
Cl1—C4	1.728 (3)	C7—O3	1.253 (3)
Cl2—C2	1.737 (3)	C7—C8	1.513 (3)
C5—O1	1.368 (3)	C8—H8A	0.9700
C5—C6	1.380 (4)	C8—H8B	0.9700
C5—C4	1.386 (4)	O3—Fe1^iv	2.1654 (17)
C4—C3	1.381 (4)	O1W—H1W	0.8200
C1—C2	1.365 (5)	O1W—H2W	0.8200
C1—C6	1.389 (4)

O3ⁱ—Fe1—O3ⁱⁱ	180.0	C6—C1—H1	120.1
O3ⁱ—Fe1—O2ⁱⁱⁱ	99.82 (6)	C5—C6—C1	120.5 (3)
O3ⁱⁱ—Fe1—O2ⁱⁱⁱ	80.18 (6)	C5—C6—H6	119.8
O3ⁱ—Fe1—O2	80.18 (6)	C1—C6—H6	119.8
O3ⁱⁱ—Fe1—O2	99.82 (6)	C1—C2—C3	121.0 (3)
O2ⁱⁱⁱ—Fe1—O2	180.0	C1—C2—Cl2	119.5 (3)
O3ⁱ—Fe1—O1W	89.36 (7)	C3—C2—Cl2	119.4 (3)
O3ⁱⁱ—Fe1—O1W	90.64 (7)	C2—C3—C4	118.8 (3)
O2ⁱⁱⁱ—Fe1—O1W	91.25 (7)	C2—C3—H3	120.6
O2—Fe1—O1W	88.75 (7)	C4—C3—H3	120.6
O3ⁱ—Fe1—O1Wⁱⁱⁱ	90.64 (7)	C5—O1—C8	117.4 (2)
O3ⁱⁱ—Fe1—O1Wⁱⁱⁱ	89.36 (7)	C7—O2—Fe1	130.51 (15)
O2ⁱⁱⁱ—Fe1—O1Wⁱⁱⁱ	88.75 (7)	O2—C7—O3	124.9 (2)
O2—Fe1—O1Wⁱⁱⁱ	91.25 (7)	O2—C7—C8	119.4 (2)
O1W—Fe1—O1Wⁱⁱⁱ	180.00 (7)	O3—C7—C8	115.7 (2)
O1—C5—C6	125.3 (2)	O1—C8—C7	114.6 (2)
O1—C5—C4	116.1 (2)	O1—C8—H8A	108.6
C6—C5—C4	118.6 (3)	C7—C8—H8A	108.6
C3—C4—C5	121.3 (3)	O1—C8—H8B	108.6
C3—C4—Cl1	119.6 (2)	C7—C8—H8B	108.6
C5—C4—Cl1	119.0 (2)	H8A—C8—H8B	107.6
C2—C1—C6	119.7 (3)	C7—O3—Fe1^iv	139.91 (16)
C2—C1—H1	120.1	H1W—O1W—H2W	112

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z+1; (iv) −x, y−1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O1^v	0.82	2.41	3.051 (3)	135
O1W—H2W···O3ⁱⁱⁱ	0.82	2.08	2.797 (3)	145

Symmetry codes: (iii) −x, −y+1, −z+1; (v) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	[Fe(C₈H₅Cl₂O₃)₂(H₂O)₂]
M_r	531.92
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	17.604 (2), 7.3122 (8), 8.0312 (9)
β (°)	94.258 (2)
V (Å³)	1031.0 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.29
Crystal size (mm)	0.23 × 0.21 × 0.20

Data collection
Diffractometer	Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.756, 0.782
No. of measured, independent and observed [I > 2σ(I)] reflections	5059, 1849, 1675
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.097, 1.05
No. of reflections	1849
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.48

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

Fe1—O3ⁱ	2.1654 (17)	Fe1—O1W	2.2297 (18)
Fe1—O2	2.1697 (16)

O3ⁱ—Fe1—O2	80.18 (6)	O3ⁱⁱ—Fe1—O1W	90.64 (7)
O3ⁱⁱ—Fe1—O2	99.82 (6)	O2ⁱⁱⁱ—Fe1—O1W	91.25 (7)
O3ⁱ—Fe1—O1W	89.36 (7)	O2—Fe1—O1W	88.75 (7)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) x, −y+1/2, z+1/2; (iii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1W—H1W···O1^iv	0.82	2.41	3.051 (3)	135
O1W—H2W···O3ⁱⁱⁱ	0.82	2.08	2.797 (3)	145

Symmetry codes: (iii) −x, −y+1, −z+1; (iv) x, −y+3/2, z+1/2.

Acknowledgements

The authors acknowledge South China Normal University for supporting this work.

References

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